Etch of silicon nitride selective to silicon and silicon dioxide useful during the formation of a semiconductor device

ABSTRACT

A method for etching silicon nitride selective to silicon dioxide and silicon (polycrystalline silicon or monocrystalline silicon) comprises the use of oxygen along with an additional etchant of either CHF 3  or CH 2 F 2 . Flow rates, power, and pressure settings are specified.

This is a continuation of U.S. Ser. No. 10/819,517 filed May 6, 2004 and issued Jun. 13, 2006 as U.S. Pat. No. 7,060,629, which is a continuation of U.S. Ser. No. 09/854,206 filed May 11, 2001 and issued Apr. 6, 2004 as U.S. Pat. No. 6,716,759.

FIELD OF THE INVENTION

This invention relates to the field of semiconductor manufacture and, more particularly, to an etch useful for removing silicon nitride selective to silicon and silicon dioxide.

BACKGROUND OF THE INVENTION

During the manufacture of semiconductor devices such as a memory devices, logic devices, and microprocessors, various processes are commonly performed. Etching silicon nitride selective to silicon (such as polysilicon) and to silicon dioxide with various etch ratios is often required. For example, hot phosphoric acid isotropically etches silicon nitride selective to silicon dioxide and silicon. Other processes for etching Si₃N₄ selective to SiO₂ and Si are discussed in “Highly Selective Etching of Silicon Nitride Over Silicon and Silicon Dioxide,” J. Vac. Sci. Technol. A 17(6), November/December 1999, which describes the use of oxygen (O₂) and nitrogen (N₂) in combination with CF₄ or NF₃. The processes discussed achieve Si₃N₄ to Si and to SiO₂ etch rate ratios of up to 100 and 70 respectively using nitrogen trifluoride. The processes use high flow rates of 800 standard cubic centimeters (sccm) O₂ and 110 sccm N₂ for most experiments. Further, using carbon tetrafluoride, a Si₃N₄ to polysilicon etch ratio of 40 was achieved while SiO₂ was not etched at all. Etch rates of silicon nitride are below about 50 angstroms (Å) per minute.

As semiconductor manufacture typically requires high volume processing to lower costs, any decrease in temporal processing requirements can result in a large increase in product throughput. Further, having options available to accomplish a task such as etching silicon nitride is advantageous, as one process may function better for certain manufacturing flows. Additional methods for etching silicon nitride selective to silicon and silicon nitride at an accelerated rate would be desirable.

SUMMARY OF THE INVENTION

The present invention provides a new etch method which, among other advantages, reduces problems associated with the manufacture of semiconductor devices, particularly problems in etching silicon nitride selective to silicon and silicon dioxide. In accordance with one embodiment of the invention a semiconductor wafer substrate assembly having a layer of silicon nitride and a layer of at least one of silicon and silicon dioxide is placed into an etch chamber. Oxygen and either CHF₃ or CH₂F₂ are introduced into an etch chamber under controlled flow rates, power, and pressure. At the parameters detailed herein, the etch removes silicon nitride selective to silicon dioxide and silicon.

Additional advantages will become apparent to those skilled in the art from the following detailed description read in conjunction with the appended claims and the drawings attached hereto.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a cross section of a semiconductor wafer assembly including a blanket layer of silicon nitride; and

FIG. 2 depicts the cross section of FIG. 1 subsequent to an etch to form silicon nitride spacers.

It should be emphasized that the drawings herein may not be to exact scale and are schematic representations. The drawings are not intended to portray the specific parameters, materials, particular uses, or the structural details of the invention, which can be determined by one of skill in the art by examination of the information herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

A silicon nitride etch selective to silicon (such as monocrystalline or polycrystalline silicon) and to silicon dioxide comprises the use of O₂ and either CHF₃ or CH₂F₂ at relatively low flow rates. It should be noted that the parameters described herein are optimized for an Applied Materials 5000 (AME5000) etcher, but they may be converted easily by one of ordinary skill in the art for other systems.

In accordance with one embodiment of the invention, a semiconductor wafer having a layer of silicon nitride and a layer of silicon dioxide and/or silicon is placed into an etch chamber and subjected to an etch. This embodiment of the etch comprises an O₂:CHF₃ or O₂:CH₂F₂ flow rate ratio of greater than about 3:1, which results in a relatively rapid, controllable Si₃N₄ etch rate with good selectivity to Si and to SiO₂. For example, an O₂ flow rate of between about 20 sccm and about 80 sccm and a CHF₃ or CH₂F₂ flow of between about 5 sccm and about 25 sccm would be sufficient. More preferably, an O₂ flow rate of between about 35 sccm and about 60 sccm and a CHF₃ or CH₂F₂ flow of between about 10 sccm and about 20 sccm would be sufficient, and most preferably an O₂ flow rate of about 60 sccm and a CHF₃ or CH₂F₂ flow of about 20 sccm would be sufficient.

During the etch, a pressure of between about 10 millitorr to about 60 millitorr is maintained. More preferably, a pressure of between about 30 to about 60 millitorr, and most preferably, between about 30 to about 40 millitorr is maintained. Further, a power of between about 300 watts to about 600 watts, more preferably between about 300 watts to about 500 watts, and most preferably between about 300 to about 400 watts sustained within the chamber. With increasing power and/or pressure the etch rate increases and the selectivity to Si and SiO₂ decreases.

Using the parameters described above, it is estimated that an Si₃N₄:SiO₂ etch ratio of up to about 1.3:1 on a blanket film and up to about 3:1 over topography can be achieved, as well as an Si₃N₄:Si etch ratio of up to about 7:1. As the O₂:CHF₃ or O₂:CH₂F₂ increases beyond 3:1 the etch rate of the Si₃N₄ decreases and the selectivity to Si and SiO₂ increases. With a high O₂:CHF₃ or O₂:CH₂F₂ ratio, above about 10:1, the etch rate becomes so slow as to be decreasing usefulness in most instances. As the O₂:CHF₃ or O₂:CH₂F₂ ratio decreases further below 3:1 the etch removes Si₃N₄ at an increased rate but also becomes less selective to Si and SiO₂. An O₂:CHF₃ or O₂:CH₂F₂ ratio of about 3:1 is believed to provide a good balance between nitride etch rate and selectivity to Si and SiO₂ in many uses of the invention for semiconductor manufacture.

At a pressure of about 30 millitorr, a power of 300 watts, a CHF₃ or CH₂F₂ flow rate of 20 sccm, and an O₂ flow rate of 60, the etch rate of Si₃N₄ will be about 420 Å/min. With a pressure of 40 millitorr, a pressure of about 40 millitorr, a power of 300 watts, a CHF₃ or CH₂F₂ flow rate of about 10 sccm and an O₂ flow rate of about 40 sccm, the etch rate increases to about 904 Å/min. As the CHF₃/O₂ or CH₂F₂/O₂ ratio increases the Si₃N₄ etch rate increases, such that at a pressure of 30 millitorr and a power of 300 watts, and a flow rate of 35 sccm for both O₂ and CHF₃ or CH₂F₂ the etch rate increases to about 1270 Å/min. These processes use a chuck temperature of about 10° C. and a sidewall temperature of about 20° C.

Using the preferred parameters of the instant invention as discussed above results in an anisotropic nitride etch which removes nitride from horizontal surfaces faster than it removes nitride from vertical surfaces at an etch ratio of about 3.7:1. This is especially useful for etching structures similar to those depicted in FIGS. 1 and 2, as it allows sufficient etching to remove the nitride layer from the wafer surface without damaging the silicon wafer. The structure of FIG. 1 depicts a semiconductor substrate assembly 10 comprising a semiconductor wafer 12, field oxide 14, doped transistor source/drain regions 16 within the wafer 12, and a transistor gate stack comprising gate oxide 18, polycrystalline silicon (polysilicon) 20, a conductive silicide layer 22, and an oxide or nitride layer 24, for example tetraethyl orthosilicate (TEOS) or silicon nitride. FIG. 1 further depicts a blanket silicon nitride layer 32 between about 300 Å about 600 Å thick. Such a structure can be manufactured by one of ordinary skill in the art.

The structure of FIG. 1 is subjected to an inventive etch as described above. An exemplary etch includes processing the wafer in a chamber of an AME5000 etch chamber. After placing the wafer substrate assembly in the etch chamber, O₂ and CHF₃ or CH₂F₂ are introduced into the chamber at flow rates of about 60 sccm and about 20 sccm respectively. Pressure is maintained at between about 30 millitorr and about 40 millitorr, and a power of between about 300 watts and about 400 watts is utilized. At a chuck temperature of about 10° C. and a sidewall temperature of about 20° C., the silicon nitride will etch at a rate of about 720 Å/min in the vertical direction, and about 180 Å/min in the horizontal direction. Generally, the vertical:horizontal etch rate will be about 4:1. For the 525 Å thick layer of silicon nitride depicted in FIG. 1, the etch is performed for between about 35 seconds and about 60 seconds which results in the structure of FIG. 2. Spacers 32 having a width of about 300 Å to about 400 Å are formed.

The etch detailed above provides a silicon nitride etch which is selective to silicon and silicon dioxide. This is accomplished using the etch as described consisting essentially of a flow of O₂ and CHF₃ or CH₂F₂. The addition of hydrogen from CHF₃ or from CH₂F₂, in addition to providing an etch of silicon nitride selective to silicon and silicon dioxide, further provides an etch which results in a more square profile of the completed transistor structures than conventional etches. The relatively low flow rates of CHF₃ or CH₂F₂ may also contribute to the less rounded feature profile compared with conventional etches having high gas flow rates. Rounded profiles may adversely affect the self-aligned contact (SAC) etch performance, and possibly affect the electrical properties of the device. In extreme cases, conventional etches can expose the conductive polysilicon, metal, or silicide which is protected by the oxide. Additionally, the structure depicted in FIG. 1, and other similar structures, can be etched with less concern for damaging the silicon wafer once the nitride has been cleared due to the high selectivity to silicon.

A semiconductor device formed in accordance with the invention may be attached along with other devices to a printed circuit board, for example to a computer motherboard or as a part of a memory module used in a personal computer, a minicomputer, or a mainframe. A device formed in accordance with the invention could further be useful in other electronic devices related to telecommunications, the automobile industry, semiconductor test and manufacturing equipment, consumer electronics, and virtually any consumer or industrial electronic equipment.

While this invention has been described with reference to illustrative embodiments, this description is not meant to be construed in a limiting sense. Various modifications of the illustrative embodiments, as well as additional embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments as fall within the true scope of the invention. 

1. A method of forming a circuit structure comprising: forming a first layer from a material selected from the group consisting of silicon and silicon dioxide over a semiconductor wafer substrate assembly; forming a second layer comprising silicon nitride on the first layer; placing the semiconductor wafer substrate into an etch chamber; introducing an etchant consisting essentially of oxygen and one of CH₂F₂ and CHF₃ into the etch chamber at a flow rate ratio of about 3:1 to etch at least a portion of the second layer, wherein the etchant etches through the second layer and stops on the first layer.
 2. The method of claim 1 further comprising introducing oxygen into the chamber at a flow rate of between about 20 sccm to about 80 sccm and introducing the one of CH₂F₂ and CHF₃ into the etch chamber at a flow rate of between about 5 sccm to about 25 sccm.
 3. The method of claim 2 further comprising maintaining a pressure of between about 10 millitorr and about 60 millitorr during the introduction of the etchant.
 4. The method of claim 3 further comprising sustaining a power of between about 300 watts and about 600 watts during the introduction of the etchant.
 5. A method of etching silicon nitride selective to at least one of silicon and silicon dioxide, comprising: forming a first layer from a material selected from the group consisting of silicon and silicon dioxide over a semiconductor wafer substrate assembly; forming a second layer comprising silicon nitride on the first layer; placing the semiconductor wafer substrate into an etch chamber; introducing an etchant consisting essentially of oxygen and CH₂F₂ into the etch chamber at a flow rate ratio of about 3:1 to etch at least a portion of the second layer, wherein the etchant etches through the second layer and stops on the first layer.
 6. The method of claim 5 wherein the oxygen is introduced into the chamber at a flow rate of between about 20 sccm to about 80 sccm and the CH₂F₂ is introduced into the etch chamber at a flow rate of between about 5 sccm to about 25 sccm.
 7. The method of claim 6 further comprising maintaining a pressure of between about 10 millitorr and about 60 millitorr during the introduction of the etchant.
 8. The method of claim 7 further comprising sustaining a power of between about 300 watts and about 600 watts during the introduction of the etchant. 